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Solution infiltration of palladium into MOF-5: synthesis, physisorption and

catalytic properties{
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Michal Sabo,a Antje Henschel,a Heidrun Fröde,a Elias Klemmb and Stefan Kaskel*a
Received 30th April 2007, Accepted 21st June 2007
First published as an Advance Article on the web 13th July 2007
DOI: 10.1039/b706432b

Palladium was infiltrated into the highly porous metal–organic framework MOF-5 {[Zn4O(bdc)3],
bdc = benzene-1,4-dicarboxylate} using [Pd(acac)2] (acac = acetylacetonate) as the precursor in
chloroform solution via ‘incipient wetness’ impregnation. The specific surface area decreases from
2885 m2 g21 to 958 m2 g21 after infiltration. After reduction in hydrogen or under vacuum, the
hydrogen adsorption capacity is increased from 1.15 wt% to 1.86 wt% at 1 atm and 77 K. The
palladium loaded MOF-5 has a high catalytic activity in styrene hydrogenation comparable to
that of palladium on activated carbon, but cis-cyclooctene hydrogenation is considerably slower.
Even at room temperature, the catalyst is not stable in air due to the low hydrothermal stability of
the MOF-5 support.

Introduction with 1,4-phenylene groups of the bdc linker resulting in a

three-dimensional cubic network.
In recent years, metal–organic frameworks have received Recently, chemical vapour infiltration of organometallic
considerable attention as a new class of porous materials with compounds was demonstrated to be a highly efficient tool for
extremely high specific surface areas and specific micropore the deposition of different metals including platinum and
volumes unattained so far in traditional adsorbents such as palladium.12,18,19 Our interest was to develop a solution based
zeolites and activated carbons.1–8 Apparent specific surface synthesis strategy for the deposition of metals inside MOFs as
areas exceeding 4000 m2 g21 have been reported.6,9 Even an alternative for gas phase deposition avoiding the use of
though the application of BET or Langmuir theory is limited, highly reactive and air sensitive precursors. In the following,
the specific micropore volume of up to 2 cm3 g21 is remarkable we describe the incipient wetness infiltration method of
and renders such systems as promising porous materials for palladium into MOF-5 leading to a highly active catalyst for
gas storage, separation and catalytic applications. hydrogenation reactions. The incorporation also significantly
In particular the application in hydrogen storage was changes the physisorption properties for nitrogen and hydro-
emphasized,10 and storage capacities exceeding 7 wt% were gen. However, even though MOF-5 is a thermally highly stable
reported at 77 K for MOF-177.11 The application of metal–
organic frameworks in catalysis is still not fully explored.
Several groups have shown the applicability of such materials
in various reactions such as the cyanosilylation, hydrogena-
tion, polymerization, and isomerization.1,12–15 Chiral MOFs
were proposed for enantioselective separations and catalytic
transformations.4,16
MOF-5 [Zn4O(bdc)3, bdc = benzene-1,4-dicarboxylate] is a
highly crystalline microporous coordination polymer.2,17 The
Zn4O-cluster represents the central part of this structure
(Fig. 1). Oxygen atoms are located in the centre of the
tetrahedron coordinated by four zinc atoms that are posi-
tioned at the tetrahedra vertices. The edges of these tetrahedra
are bridged by six carboxylate groups of the organic linker
forming an octahedral node. The nodes are linked together

a
Department of Inorganic Chemistry, Technical University Dresden,
Mommsenstr. 6, D-01069, Dresden, Germany.
E-mail: stefan.kaskel@chemie.tu-dresden.de; Fax: +49 351 4633 7287;
Tel: +49 351 4633 4885
b
Department of Chemical Technology, Chemnitz University of
Technology, Strasse der Nationen 62, D-09111 Chemnitz, Germany
{ Electronic supplementary information (ESI) available: MOF-5
hydrolysis: decrease in the specific BET surface area; moisture
influence and powder X-ray diffractograms. See DOI: 10.1039/ Fig. 1 3D model of MOF-5. The large central grey sphere represents
b706432b the void in the MOF-5 structure.

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material, it will be shown that the applicability of MOF-5 as a Catalytic investigation

support is seriously limited due to its low chemical stability.
Hydrogenation reactions were carried out in solution in a
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static hydrogen atmosphere (1 atm) at 35 uC for 24 h. The

Experimental
General
The materials studied were synthesized and treated under an
argon atmosphere, using a vaccum line or a glovebox. The
chemicals Pd/C (1 wt% Pd) and Pd(acac)2 (99%) were purchased
from Aldrich, the Zn(NO3)2?4H2O (98.5%) and terephthalic
acid (98%) were purchased from Acros, the Norit A was
purchased from Serva and the solvent CHCl3 (99.8%) from
Merck and stored over a 4 Å molecular sieve. Diethylformamide
(DEF) and dimetylformamide (DMF) were purchased from
Merck, dried over CaH2 in argon for 12 h, purified by
distillation, and stored over a 4 Å molecular sieve in argon.
Synthesis of MOF-5.19 Zn(NO3)2?4H2O (8.3200 g,
31.824 mmol) and H2bdc (1.7600 g, 10.594 mmol) were
dissolved in DEF (100 cm3). The solution was heated to 100 uC
in a Teflon-lined stainless-steel autoclave at a rate of
1.5 uC min21 for 20 h and then cooled to room temperature
at a rate of 0.5 uC min21. The solutions were filtered off in
argon flow, and the clear block crystals were washed in DMF
and exchanged with dry CHCl3 thrice in three days. Finally,
the material was evacuated for 12 h to remove chloroform
molecules and stored in a glovebox.
Synthesis of Pd/MOF-5
Pd(acac)2/MOF-5. The solution of Pd(acac)2 (0.0143 g,
0.134 mmol) dissolved in chloroform (0.58 cm3) was slowly
drop-wise added to guest-free MOF-5 (0.4937 g, 0.64 mmol)
under continuous stirring forming an orange paste. The
solvent was first slowly evaporated for 2 h in an argon
atmosphere while the paste was continuously stirred. The pre-
dried paste was finally completely dried under reduced
pressure (2.27 6 1025 atm) overnight at room temperature
to yield a fine slightly yellow powder of Pd(acac)2 deposited on
MOF-5.
Pd/MOF-5. 100 mg of the dried powder Pd(acac)2/MOF-5
was filled in a glass tube and heated under vacuum at 150 uC or
200 uC for 4 h to produce samples a and b, respectively.
Samples c and d were obtained by heating 100 mg in H2 flow at
150 uC or 200 uC for 1 h, respectively. After the reduction
procedures, the samples were washed with chloroform to
remove soluble decomposition products and evacuated at
125 uC overnight under reduced pressure. A portion of the
desolvated solid was added to NaOH in D2O and subjected to
1
H and 13C NMR measurements. 1H NMR (500 MHz, D2O,
25 uC, TMS): d = 7.74 ppm, 13C NMR d = 128.44 ppm
(Caromatic), 138.51 ppm (Cipso), 175.23 ppm (Ccarboxylate).
catalyst to substrate weight ratio was 1 : 100. Typically 0.050 g
catalyst and 5.00 g substrate were used. For the leaching test,
the reaction mixture was filtered using a 0.2 mm PTFE filter at
28 wt% conversion at 35 uC, the catalyst was separated, and
the supernatant was allowed to react further in a separate vial
under the same reaction conditions.
Instrumentation
X-Ray diffraction (XRD) patterns were obtained in transmis-
sion geometry using a Stoe StadiP X-ray diffractometer with
IPDS detector and CuKa1 (l = 0.15405 nm) radiation (40 kV,
30 mA). Nitrogen physisorption isotherms were measured at
77 K using a Quantachrome AUTOSORB 1 C apparatus. The
catalytic reactions were monitored using a Shimadzu GCMS-
QP5000 equipped with non-polar polysilphenylene–siloxane
column BPX5 from SGE. Specific surface areas were calcu-
lated using the single point BET20 plot at p/p0 = 0.1 and all
specific micropore volumes were measured at p/p0 = 0.2.
Results and discussion
The integration of palladium into MOF-5 (Pd/MOF-5) was
achieved using incipient wetness impregnation of a palladium
precursor solution [Pd(acac)2, acac = acetylacetonate].
The synthesis of Pd/MOF-5 was carried out in three steps. The
catalyst support (MOF-5) was synthesized in a first step by
modified procedures reported by Millward and Yaghi.17 In the
second step, the guest-free MOF-5 was impregnated with chloro-
form solution of Pd(acac)2 via the ‘incipient wetness’ method. In
the last step, Pd(acac)2/MOF-5 was reduced under vacuum or
using hydrogen flow at different temperatures (‘activation step’).
The different reduction conditions were necessary to optimize
the catalyst performance. All products of the different steps
were characterized by powder X-ray diffraction (PXRD) and
by nitrogen physisorption. The catalytic activity was tested
for styrene, 1-octene and cis-cyclooctene in a static hydrogen
atmosphere always under the same conditions (Scheme 1).
The catalytic activity of Pd/MOF-5 was compared with
Pd/Norit A and Pd/C (Aldrich), with 1 wt% Pd content for all
three catalysts.
Support characterization
Porosity measurements of the MOF-5 support were performed
using nitrogen physisorption at 77 K. Fig. 2 shows the nitrogen
adsorption and desorption isotherm of the pure support
MOF-5 obtained after chloroform exchange and degassing
under vacuum at 140 uC.

Pd/Norit A. The solution of Pd(acac)2 (0.0146 g, 0.137 mmol)

dissolved in chloroform was added to the 1 g of Norit A (Vg =
0.41 cm3 g21, Sg = 984 m2 g21). The following steps were
carried out in the same way as for Pd/MOF-5 (sample d). The
impregnation of crude product was performed twice to obtain
Pd/Norit A with 1 wt% Pd content. Scheme 1 Hydrogenation of styrene (1 atm).

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Fig. 2 Nitrogen adsorption isotherm of MOF-5 ($) and Pd/MOF-5

sample d (&) measured at 77 K. Empty squares/circles represent the
desorption isotherm.

The measurement shows a type I isotherm and the specific

micropore volume calculated from the adsorption branch of
the isotherm is 1.18 cm3 g21. The apparent specific BET
surface area is 2885 m2 g21. These values are comparable
with results reported earlier.17 The XRD powder patterns of
miscellaneous treatment states of MOF-5 are shown in Fig. 3.
There is no difference between theoretical calculated and the
guest-free MOF-5 patterns, respectively.
However, the guest-free MOF-5 framework decomposes in
the presence of moisture when the activated sample is exposed
to air (ESI{). For testing the hydrothermal stability, the
support was placed in a closed glass vessel and a second
smaller vial filled with water was placed underneath the dry
powder. In this manner, the sample was exposed for 48 h at
Fig. 3 Powder X-ray diffractograms of MOF-5: calculated pattern
room temperature to an atmosphere saturated with water (A), MOF-5 without guests (B), MOF-5 impregnated with Pd(acac)2
steam, which is a very mild hydrothermal treatment. However, (C), and Pd/MOF-5 sample d (D). The dashed line represents the first
the XRD pattern of the moisture exposed MOF-5 is reflection of metallic palladium.22
completely different from that of MOF-5 (Fig. 4). The N2
physisorption is also significantly lower, the specific BET
surface area decreases to 11 m2 g21. Thus, MOF-5 should be
considered as extremely moisture sensitive which explains the
huge variations in surface areas reported by different groups
and the bad reproducibility of some synthesis procedures.17,21
For all tests and further treatments, careful handling of the
sample under a protective atmosphere is necessary to achieve
reproducible results.

Pd(acac)2/MOF-5
Incipient wetness impregnation was carried out with chloro-
form solution of Pd(acac)2 (1 wt% Pd). The volume of this
solution used for the impregnation was calculated from the
Fig. 4 Powder X-ray patterns of guest-free MOF-5 (bottom) and
value of the micropore volume. The three-dimensional crystal-
after 48 h exposition in a water atmosphere (top).
line order of the MOF host lattice remains unchanged after
loading with Pd(acac)2, as shown by the comparison of the
200 uC under vacuum, respectively. Samples c and d were
PXRD pattern before and after impregnation (Fig. 3B and 3C,
reduced in hydrogen flow at 150 and 200 uC, respectively.
respectively).
When the hydrogen reduction method was used, no hydro-
genation of the benzene-1,4-dicarboxylate linker was observed
Pd/MOF-5
which was confirmed by the 1H and 13C NMR spectra of
The last step was the reduction of Pd(acac)2/MOF-5. Four dissolved Pd/MOF-5 (Experimental section).
samples of Pd/MOF-5 were prepared using different reduction The powder XRD patterns (Fig. 3) do not show a difference
conditions (Table 1). Samples a and b were reduced at 150 and between the calculated powder patterns of MOF-5 and

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Table 1 Specific surface area of different Pd/MOF-5 samples
Sample Reduction conditions Sg/m2 g21
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MOF-5 ——— 2885
Pd/MOF-5 a Vacuum; 150 uC 718
Pd/MOF-5 b Vacuum; 200 uC 894
Pd/MOF-5 c H2 flow; 150 uC 779
Pd/MOF-5 d H2 flow; 200 uC 958
Pd/MOF-5d. Only differences in the reflection intensities
and the color of the resulting materials are observed. We
could not unambiguously identify additional reflections of
palladium in the sample, which is reasonable due to the
low degree of loading. According to our physisorption data,
after impregnation, the material is still microporous (type I
isotherm, Fig. 2), however, the specific BET surface area (and
the pore volume) decreased significantly from 2885 m2 g21
(Vm: 1.18 cm3 g21) for pure MOF-5 to 958 m2 g21 in Pd/MOF-
5d (Vm: 0.39 cm3 g21). Taking the low amount of loading
into account, the significant decrease of surface area also
indicates partial decomposition of the sample. The results
of the elemental analysis are in good agreement with the
expected values calculated for 1 wt% Pd/MOF-5: wt% obs.
¡ s (calc.): C: 36.89 ¡ 0.11 (36.96); H: 1.91 ¡ 0.06 (1.55);
O: 26.85 ¡ 0.18 (26.67); Zn: 31.39 ¡ 0.36 (33.54); Pd:
1.04 ¡ 0.01.
Hydrogen storage
The hydrogen storage properties were also investigated for
Pd/MOF-5. A gravimetric uptake of 1.32 wt% H2 was reported
for MOF-5 at 1 atm and 77 K.23 According to our volumetric
data 1.15 wt% are adsorbed for our MOF-5 support under the
same conditions. Recently, a significantly increased storage
capacity was observed by mixing a solid platinum catalyst
(supported on activated carbon) with MOF-5 at a ratio of 1 : 9.
The enhanced storage capacity was attributed to dissociation
causing a primary spillover at the Pt catalyst and MOF-5
acting as a secondary spillover receptor.24,25
According to our data a similar effect is observed for
microporous MOF-5 impregnated with 1 wt% palladium
leading to an increase of reversible hydrogen storage up to
1.86 wt% at 1 bar and 77 K (Fig. 5). However, the increase at
Fig. 5 Hydrogen adsorption at 77 K for MOF-5 ($) and Pd/MOF-5
sample d (&). Empty squares/circles represent the desorption isotherm.
3830 | J. Mater. Chem., 2007, 17, 3827–3832
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Fig. 6 Pd/MOF-5 catalysed ethylbenzene formation from styrene
hydrogenation. Sample a ($), b (¤), c (m) and d (&).
low pressures does not necessarily imply a higher capacity at
high pressures and the slope of the adsorption curve is steeper.
Hydrogenation
The main focus of this work was to find suitable conditions for
an efficient integration of palladium into MOF-5 for catalytic
applications. The substrates used for catalytic tests were
styrene, 1-octene and cis-cyclooctene. For catalyst optimiza-
tion, styrene was the chosen substrate.
Fig. 6 displays the formation of ethylbenzene in Pd/MOF-5
catalysed styrene hydrogenation. After 12 h all four Pd/MOF-
5 catalysts convert more then 99.7 wt% of the styrene to
ethylbenzene. The hydrogenation using samples a and b
(reduced at 150 uC or 200 uC under vacuum, respectively)
produced less than 85 wt% ethylbenzene after 8 h. The
reduction of Pd/MOF-5 in H2 flow (at 150 uC for sample c and
200 uC for sample d) showed a positive influence on catalytic
performance. The concentration of ethylbenzene after 8 h was
97 wt% when sample c was used in the reaction and 94 wt%
when sample d catalysed the styrene hydrogenation.
In a second hydrogenation experiment we used 1-octene as
the substrate to compare the catalytic activity and selectivity.
The main problem of 1-alkene hydrogenation with palladium
is the production of isomers as by-products. On the other
hand, cracking does not occur. However, it is more probable
that the double bond leads to the occurrence of cis/trans
isomers of 2-, 3- and 4-alkenes. The concentration of 1-octene
after 9 h was less then 0.2 wt% for all samples (Fig. 7).
The third hydrogenation experiment was carried out with
cis-cyclooctene as the substrate to compare the catalytic
features of Pd/MOF-5. The reason for this choice was the
different molecular constitution, for probing the accessibility
of the pore system. A second advantage is that isomerization
does not lead to a complex mixture of products. Additionally a
comparison with earlier work is possible.12
The kinetic profile of cyclooctane formation displayed in
Fig. 8 shows a different kinetic profile for the hydrogenation.
Possible reasons for this difference are, first, the different
activation energies for the hydrogenation of styrene as
compared to cis-cyclooctene. A second reason could be the
larger kinetic diameter of cis-cyclooctene as compared to
styrene or 1-octene. Either the reason is slower diffusion
through the MOF-5 lattice as compared to styrene and
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Fig. 7 Conversion of 1-octene with Pd/MOF-5 as a function of time. Fig. 9 Weight concentration of 1-octene over Pd/MOF-5 as a
Sample a ($), b (¤), c (m) and d (&). function of time. Empty squares represent course of events after
withdrawing the catalyst.

Fig. 8 Kinetic profiles of ethylbenzene (&) and cyclooctane

(¤) formation, respectively, with Pd/MOF-5 catalysed styrene
hydrogenation.

1-octene or cis-cyclooctene cannot access the pores and the

residual low conversion is caused by active sites outside the
pore system.

Heterogeneity and reusability of Pd/MOF-5 Fig. 10 Powder XRD patterns of Pd/MOF-5 d recorded ex situ after
different durations of 1-octene hydrogenation.
To verify the heterogeneous mechanism of the catalytic
reaction over Pd/MOF-5, filtration tests were carried out for The reusability of the catalyst was tested for styrene
the 1-octene hydrogenation (Fig. 9). After 1.5 h the catalyst hydrogenation in two consecutive runs (Fig. 11). After the
was filtered off. The filtrate was again exposed to hydrogen first run (24 h), the products were distilled off from the
and the reaction was followed using GC-MS. A further reaction flask. The catalyst was dried overnight at 200 uC
decrease of 1-octene concentration was not observed as
expected for the catalyst-free solution. Thus, leaching of the
catalyst is not detected. Since Pd(acac)2 is soluble in 1-octene
and n-octane, the heterogeneity test indicates that the
Pd(acac)2 molecules are well reduced after the heat treatment
and the metallic palladium is immobilized well on the support.
The structure of Pd/MOF-5 is well preserved throughout the
reaction if all materials were handled in inert gas. Fig. 10
shows the XRD pattern of the catalyst recorded after 1.5 h and
24 h of the reaction and isolation via filtration in an inert gas
atmosphere. Only very minor differences are detected and the
XRD patterns were almost identical. However, if the XRD
pattern of the used catalyst is recorded in air, the pattern
changes significantly (not shown) indicating immediate
decomposition similar as in the case of the hydrothermal Fig. 11 Ethylbenzene formation in 1st run (&), 2nd run ($), and 3th
treatment (above). run (m) in the Pd/MOF-5 catalysed hydrogenation of styrene.

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Fig. 12 Ethylbenzene formation with different palladium supported
catalysts. & represents hydrogenation with Pd/MOF-5 (1 wt%), #
represents Pd/Norit A (1 wt%), and D shows the hydrogenation with
Pd/C (1 wt%).
under vacuum and used for a second hydrogenation of styrene.
The same procedure was repeated for the third run. In the
second hydrogenation the conversion after 18 h stays constant
at 99 wt% ethylbenzene compared to the first run. In the third
run, the ethylbenzene concentration decreases to 95 wt% after
18 h and 98 wt% after 24 h, respectively. Thus, the catalyst can
be reused several times but some degree of deactivation and
reduced performance is observed as well.
Catalytic properties of Pd on different supports
In Fig. 12, the hydrogenation activity of Pd/MOF-5 (1 wt%)
is compared with that of Pd/C (1 wt%) and Pd/Norit A
(1 wt%). Norit A is a microporous carbon and Pd/Norit A
was synthesized via the same incipient wetness method as
for Pd/MOF-5 described herein before. Before starting the
hydrogenation, the carbon samples were activated under
similar conditions as Pd/MOF-5 sample d. It is evident that
for the same content of Pd the catalytic activity of Pd/MOF-5d
after 8 h of styrene hydrogenation is higher (94 wt% ethyl-
benzene) as compared with Pd/Norit A (76 wt% ethylbenzene)
and Pd/C (54 wt% ethylbenzene), respectively. However, the
advantage of MOF-5 or MOFs in general can be seen in the
highly ordered and crystalline structure as compared to
activated carbon with an irregular structure and a pore size
distribution in the micropore regime. A disadvantage of
MOF-5 is clearly the low chemical stability and sensitivity
against moisture. Thus, a key issue for our future studies
will be to identify MOFs with a higher chemical stability
and robustness allowing for a broader range of catalytic test
reactions.
Conclusions
We have shown incipient wetness impregnation to be a
valuable alternative for the synthesis of palladium loaded
3832 | J. Mater. Chem., 2007, 17, 3827–3832
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microporous coordination polymers. Pd/MOF-5 has a high
catalytic activity in styrene hydrogenation. Moreover, the
material shows a high hydrogen adsorption capacity up to
1.86 wt% with reversible desorption and a significant increase
as compared to palladium-free MOF-5. The Pd supported on
MOF-5 showed higher catalytic activity in comparison with Pd
supported on activated carbon. The catalyst is stable during
the hydrogenation reaction and can be reused several times,
however due to the low hydrothermal stability careful handling
under inert conditions limits the practical applicability of
Pd/MOF-5 significantly.
References
1 S. Kitagawa, R. Kitaura and S. Noro, Angew. Chem., Int. Ed.,
2004, 43, 2334–2375.
2 H. Li, M. Eddaoudi, M. O’Keeffe and O. M. Yaghi, Nature, 1999,
402, 276–279.
3 S. S. Y. Chui, S. M. F. Lo, J. P. H. Charmant, A. G. Orpen and
I. D. Williams, Science, 1999, 283, 1148–1150.
4 D. N. Dybtsev, H. Chun and K. Kim, Angew. Chem., Int. Ed.,
2004, 43, 5033–5036.
5 M. Eddaoudi, D. B. Moler, H. L. Li, B. L. Chen, T. M. Reineke,
M. O’Keeffe and O. M. Yaghi, Acc. Chem. Res., 2001, 34, 319–330.
6 G. Ferey, Science, 2005, 310, 1119–1119.
7 U. Müller, M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt
and J. Pastre, J. Mater. Chem., 2006, 16, 626–636.
8 S. Kaskel, in Handbook of Porous Solids, ed. F. Schüth, K. S. W.
Sing and J. Weitkamp, Wiley-VCH, Weinheim, 1st edn, 2002,
vol. 2, pp. 1190–1249.
9 H. K. Chae, D. Y. Siberio-Perez, J. Kim, Y. Go, M. Eddaoudi,
A. J. Matzger, M. O’Keeffe and O. M. Yaghi, Nature, 2004, 427,
523–527.
10 B. Panella, M. Hirscher, H. Putter and U. Müller, Adv. Funct.
Mater., 2006, 16, 520–524.
11 A. G. Wong-Foy, A. J. Matzger and O. M. Yaghi, J. Am. Chem.
Soc., 2006, 128, 3494–3495.
12 S. Hermes, M. K. Schroter, R. Schmid, L. Khodeir, M. Muhler,
A. Tissler, R. W. Fischer and R. A. Fischer, Angew. Chem., Int.
Ed., 2005, 44, 6237–6241.
13 L. Alaerts, E. Seguin, H. Poelman, F. Thibault-Starzyk, P. A.
Jacobs and D. E. De Vos, Chem.–Eur. J., 2006, 12, 7353–7363.
14 J. Perles, M. Iglesias, M. A. Martin-Luengo, M. A. Monge,
C. Ruiz-Valero and N. Snejko, Chem. Mater., 2005, 17, 5837–5842.
15 K. Schlichte, T. Kratzke and S. Kaskel, Microporous Mesoporous
Mater., 2004, 73, 81–88.
16 C. D. Wu, A. Hu, L. Zhang and W. B. Lin, J. Am. Chem. Soc.,
2005, 127, 8940–8941.
17 A. R. Millward and O. M. Yaghi, J. Am. Chem. Soc., 2005, 127,
17998–17999.
18 S. Hermes, F. Schroder, S. Amirjalayer, R. Schmid and
R. A. Fischer, J. Mater. Chem., 2006, 16, 2464–2472.
19 H. Kim, H. Chun, G. H. Kim, H. S. Lee and K. Kim, Chem.
Commun., 2006, 2759–2761.
20 S. Brunauer, P. H. Emmet and E. Teller, J. Am. Chem. Soc., 1938,
60, 309–319.
21 B. Panella and M. Hirscher, Adv. Mater., 2005, 17, 538–541.
22 ICCD (International Center for Diffraction Data) Card No. 5-681.
23 J. L. C. Rowsell, A. R. Millward, K. S. Park and O. M. Yaghi,
J. Am. Chem. Soc., 2004, 126, 5666–5667.
24 Y. W. Li and R. T. Yang, J. Am. Chem. Soc., 2006, 128, 726–727.
25 Y. W. Li and R. T. Yang, J. Am. Chem. Soc., 2006, 128,
8136–8137.
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